CN1078749C - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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CN1078749C
CN1078749C CN97115403A CN97115403A CN1078749C CN 1078749 C CN1078749 C CN 1078749C CN 97115403 A CN97115403 A CN 97115403A CN 97115403 A CN97115403 A CN 97115403A CN 1078749 C CN1078749 C CN 1078749C
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storage battery
oxide
lithium
complex
spinel structure
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CN1173746A (en
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山下裕久
服部康次
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Murata Manufacturing Co Ltd
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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    • C01G51/54—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [Mn2O4]-, e.g. Li(CoxMn2-x)04, Li(MyCoxMn2-x-y)O4
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    • C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
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Abstract

The invention provides a lithium secondary battery, comprising a cathode having a spinel-structured lithium-manganese complex oxide as the active material, which is characterized in that the particles of said spinel-structured lithium-manganese complex oxide are hollow, spherical secondary particles formed by sintering of primary particles, and said secondary particles have a mean particle size of from about 1 to 5 micrometer and a specific surface area of from about 2 to 10 m2/g. The lithium secondary battery has a high capacity and excellent charge-discharge cycle characteristics.

Description

Lithium storage battery
The present invention relates to lithium storage battery, specifically, relate to and containing with complex Li-Mn-oxide with spinel structure lithium storage battery as the negative electrode of active material.
Recently, portable and wireless electronic equipment becomes more and more popular.As the power supply of this equipment, press for have high-energy-density, small-sized and light storage battery.For satisfying this demand, the lithium storage battery that contains nonaqueous electrolyte has dropped into practical application.
In general, lithium storage battery comprises that one has lithium-containing compound and has as the negative electrode of active material, one and can adsorb and separator that the material (as carbonizable substance or lithium metal) of desorb lithium contains nonaqueous electrolyte or solid electrolyte as anode and one deck of active material.Lithium-containing compound as active material of cathode comprises, for example present LiCoO that uses 2, LiNiO 2And LiMn 2O 4Recently, people invest the complex Li-Mn-oxide of spinel structure, for example typical LiMn to attentiveness 2O 4, because this composite oxides can produce high Eo+, and cheap because make the cost of material of this composite oxides, thus be expected stably to obtain this composite oxides.In this case, the various lithium storage batteries of these composite oxides have been proposed to contain as active material of cathode.
For example, the disclosed patent application 94-333562 of Japan has disclosed a kind of LiMn of containing 2O 4The type compound is as the lithium storage battery of active material of cathode, and wherein this compound is a form of spherical particles, has uniform rough surface, and its median diameter is the 0.5-0.6 micron, and particle diameter is the 0.1-1.1 micron.Japan publication application 96-69790 has disclosed a kind of lithium storage battery that contains complex Li-Mn-oxide as active material of cathode, and wherein the specific area of composite oxides is 0.05-5.0m 2/ g.
But the complex Li-Mn-oxide that contains this spinel structure as the conventional lithium storage battery of active material of cathode still can not be satisfactory aspect battery capacity and the charge.
Therefore, the purpose of this invention is to provide a kind of lithium storage battery with high power capacity and good charge.
The invention provides the lithium storage battery of mentioned kind, the spherical secondary granule that the complex Li-Mn-oxide particle that it is characterized in that described spinel structure is hollow, formed by the primary granule sintering, the average grain diameter of described secondary granule is the 1-5 micron, and specific area is 2-10m 2/ g.
In above-mentioned lithium storage battery, the complex Li-Mn-oxide of described spinel structure can be used general formula Li (Mn 2-xLi x) O 4Expression, wherein 0＜x＜0.02, and Mn is partly replaced by Cr, Ni, Fe, Co or Mg.
Because lithium storage battery uses particle diameter and specific area to be controlled at the spherical hollow particle of complex Li-Mn-oxide of the spinel structure in the above-mentioned number range as active material of cathode, so nonaqueous electrolyte can infiltrate in the spherical hollow particle well, avoid decomposition simultaneously, and increased the contact area between nonaqueous electrolyte and the particle.Thereby improved the degree of utilizing of active material of cathode in the lithium storage battery of the present invention.In addition, because active material of cathode contains the relatively large secondary granule that is formed by the primary granule sintering, so it can be shaped when having suitably big specific area well.Even reduce the amount of the adhesive that adds, this material still can be shaped as the negative electrode of the unit volume energy density with increase.
In above-mentioned lithium storage battery, the complex Li-Mn-oxide of described spinel structure can be used general formula Li (Mn 2-xLi x) O 4Expression, wherein 0≤x≤0.1.
In above-mentioned lithium storage battery, the complex Li-Mn-oxide of described spinel structure can be used general formula Li (Mn 2-xLi x) O 4Expression, wherein 0＜x＜0.02.
In above-mentioned lithium storage battery, the complex Li-Mn-oxide of described spinel structure can be used general formula Li (Mn 2-xLi x) O 4Expression, wherein 0≤x≤0.1, and Mn is partly replaced by Cr, Ni, Fe, Co or Mg.
As the complex Li-Mn-oxide that is used for spinel structure of the present invention general formula Li (Mn 2-xLi x) O 4During expression, x should drop in the scope of 0≤x≤0.1, so that make the storage battery that obtains have higher energy efficiency and better charge.Best is described general formula Li (Mn 2-xLi x) O 4In x drop in the scope of 0＜x＜0.02 so that energy efficiency that the storage battery that obtains is had more increase and better charge.
In addition, also can use in the present invention by the position that replaces part manganese with any Cr, Ni, Fe, Co and/or Mg derived from Li (Mn 2-xLi x) O 4The complex Li-Mn-oxide of any other spinel structure, and obtain identical result.
Also can comprise as active material of positive electrode in the lithium storage battery of the present invention, can adsorb and the material of desorb lithium, as material with carbon element, lithium metal or lithium alloy.The nonaqueous electrolyte that is used for storage battery can be (as LiPF by electrolyte lithium salt 6, LiClO 4, LiBF 4Or LiAsF 6) be dissolved in the solution of making in the mixed solvent that contains propylene carbonate or ethylene carbonate and diethoxyethane or dimethoxy-ethane.As the separator of storage battery, can use porous polypropylene film or adhesive-bonded fabric.Also can use solid electrolyte to replace soaking into the separator of this nonaqueous electrolyte.
Fig. 1 is the SEM photo as lithium storage battery active material of cathode of the present invention;
Fig. 2 is the profile of an example of lithium storage battery of the present invention;
Fig. 3 is the curve that shows various lithium storage battery charge.
Below with reference to embodiment to the present invention preferably example be described.
Embodiment 1
Use lithium nitrate and manganese nitrate to prepare complex Li-Mn-oxide as metallic compound.With mol ratio Li/Mn is accurately weigh this lithium nitrate and manganese nitrate of 1.02/1.98, forms complex Li-Mn-oxide Li (Mn 2-xLi x) O 4, being placed in the container, adding 1000ml volume ratio is water/alcohol mixeding liquid of 1/1, and it is stirred back formation solution.
Subsequently the solution that obtains being sprayed into predetermined temperature with 1200ml/ hour speed by a nozzle is to atomize in 600-800 ℃ the vertical thermal decomposition furnace, and in this stove the powdered composite oxides of pyrolysis.Then the composite oxides that will generate place an aluminium oxide box and annealing 2 hours under 300-900 ℃ of predetermined temperature.Obtain Li (Mn in this way 1.98Li 0.02) O 4Composite oxides sample 11-15 (referring to table 1).The sample that has asterisk (*) in table 1 has exceeded scope of the present invention, and other samples are within the scope of the invention.
Except these samples, also listed the Li (Mn that obtains by melt impregnation in the table 1 1.98Li 0.02) O 4Duplicate 16.This sample is made as raw material by lithium nitrate and EMD (electrolytic manganese dioxide).With Li/Mn mol ratio 1.02/1.98 accurately weigh this lithium nitrate and EMD, subsequently in grinding in ball grinder and mix it, then 600 ℃ of calcinings 48 hours, to obtain the lithium composite oxides of melt impregnation in EMD.
In addition, also listed another Li (Mn that makes by solid reaction process in the table 1 1.98Li 0.02) O 4Duplicate 17.This sample is made as raw material by lithium carbonate and manganese carbonate.With Li/Mn mol ratio 1.02/1.98 accurately weigh this lithium carbonate and manganese carbonate, subsequently in grinding in ball grinder and mix it, then 900 ℃ of calcinings 48 hours, to obtain composite oxides.
The photo of the Powdered composite oxides that obtain above is to use scanning electron micrograph method (SEM) to obtain, and has observed the form of particle and measured particle diameter in photo.In addition, use the nitrogen adsorption method to obtain the specific area of various composite oxides.Use X-ray diffraction method (diffractometry) (XRD) to analyze composite oxides.The data that obtain are listed in table 1.In table 1, LM is meant that sample is the diffracting spectrum that the complex Li-Mn-oxide of spinel structure does not have any impurity.
The SEM photo of sample is listed in Fig. 1.Composite oxides sample 1 comprises the secondary granule that is formed by the primary granule sintering of spherical, hollow and porous as seen from Figure 1.The surface of each hollow, spherical secondary granule has many dark holes of leading to its inside.
Then, the Powdered complex oxide forming that makes is above become negative electrode, and assess its formability.Briefly, the conductor (acetylene black) of 100 weight portion active material of cathode (composite oxides), 5 weight portions and 5-20 weight portion adhesive (polytetrafluoroethylene) are kneaded and be shaped in flakes.Mixture shaping formability in blocks is listed in table 1.In table 1, " O " expression mixture has formed sheet well; " P " expression mixture is near having formed sheet; " X " expression mixture can not form sheet.
Table 1
Sample Atomization temperature (℃) Annealing temperature (℃) Grain shape Average grain diameter (micron) Specific area (m 2/g) XRD analyzes Formability, the amount (part) that adhesive adds
5 10 20
11 800 800 Hollow sphere 3.2 4.3 LM O O O
12 800 600 Hollow sphere 1.3 9.8 LM O O O
13 600 800 Hollow sphere 4.9 2.1 LM O O O
*14 800 300 Hollow sphere 1.1 25.1 LM P O O
*15 800 900 Hollow sphere 7.5 1.1 LM O O O
*16 600 (melt impregnations) Loose aggregates 1.3 5.0 LM X P O
*17 900 (solid phase reactions) Loose aggregates 1.0 7.8 LM X P O
Then use the various composite oxides that make above to prepare storage battery as active material of cathode.
Exactly, the various composite oxides of 100 weight portions, 5 weight portion conductors (acetylene black) and 5 weight portion adhesives (to sample 16 and 17, using 10 weight portion adhesives, because relatively poor by visible their formability of table 1) are kneaded and is shaped in blocks.The pressurization of every kind of sheet is sticked on the SUS screen cloth dish of 17mm diameter and make negative electrode.
Then, as shown in Figure 2, the SUS screen cloth of negative electrode 3 is combined with each other negative electrode 3 and lithium anodes 4 (diameter 17mm, thick 0.2mm) outwardly, puts into polypropylene separator 5 therebetween, and negative electrode 3 is packed into it in stainless steel cathode container 1 down.Make electrolyte immerse separator 5 subsequently.Here used electrolyte is with LiPF 6Be dissolved in volume ratio and be 1/1 propylene carbonate and 1, the concentration that makes in the mixed solvent of 1-dimethoxy-ethane is the solution of 1M.Then seal the opening of cathode container 1 by means of insulating packing 6 usefulness stainless steel anode plates 2.Thereby acquisition lithium storage battery.
Be 1.0mA/cm then in charging and discharging currents density 2, maximum charging voltage is that 4.3V, ending discharge voltage are the test that discharges and recharges of under the condition of 3.0V the lithium storage battery of acquisition like this being carried out 200 circulations.Result of the test is listed in Fig. 3.In Fig. 3, the test piece number (Test pc No.) of storage battery is same as the test piece number (Test pc No.) as the composite oxides of active material of cathode.By the data of table 1 and Fig. 3 as seen, contain the Li (Mn of spinel structure 1.98Li 0.02) O 4(it is to be 1-5 micron, specific area 2-10m by the average grain diameter that the primary granule sintering forms 2The spherical hollow secondary granule of/g) the lithium storage battery sample 11-13 as active material of cathode has high capacity and good charge.
In contrast, for containing specific area greater than 10m 2Li (the Mn of/g 1.98Li 0.02) O 4The storage battery sample 14 of particle, its charge and discharge cycles feature is poor.This is too big because of the contact area between composite oxide particle in this storage battery and the nonaqueous electrolyte, and it is serious to cause nonaqueous electrolyte to decompose.On the other hand, for containing specific area less than 2m 2The storage battery sample 15 of/g composite oxide particle, its capacity is low.This is too little because of the contact area between composite oxide particle in this storage battery and the nonaqueous electrolyte.
To composite oxides Li (Mn 1.98Li 0.02) O 4Be loose but not the storage battery sample 16 of hollow sphere particle, its capacity is low.This be because the contact area between composite oxides and the nonaqueous electrolyte can not be big satisfactory, in addition because the formability official post of material must be difficult to improve the ratio of active material in negative electrode.
Composite oxides Li (Mn in the storage battery sample 17 1.98Li 0.02) O 4As sample 16, be loose.Therefore, the capacity of storage battery sample 17 be low and charge-discharge characteristic relatively poor.This is big unsatisfactorily because of the contact area between composite oxides in this storage battery and the composite oxides, because the feasible ratio that is difficult to improve active material in this storage battery negative electrode of the formability of this material difference, in addition, because this oxide forms by solid phase reaction, so used combined oxidation compositions is uneven.
Embodiment 2
With lithium nitrate and manganese nitrate as the metallic compound that constitutes complex Li-Mn-oxide.Accurately weigh these lithium nitrates and manganese nitrate form the general formula Li (Mn shown in the table 2 2-xLi x) O 4The various complex Li-Mn-oxides of (wherein 0≤x≤0.1) are placed in the container, add the 1000ml volume ratio and be the mixed liquor of water/ethanol of 1/1, it is stirred form solution.
Subsequently the solution that obtains being sprayed into predetermined temperature with 1200ml/ hour speed by a nozzle is to atomize in 700 ℃ the vertical thermal decomposition furnace, and in this stove the powdered composite oxides of pyrolysis.Then the composite oxides that will generate place an aluminium oxide box and 700 ℃ of annealing 2 hours.Obtain the composite oxides sample 21-28 shown in the table 2 in this way.
The photo of the Powdered composite oxides that obtain above is to use scanning electron micrograph method (SEM) to obtain, and measures particle grain size on photo.In addition, use the nitrogen adsorption method to obtain the specific area of various composite oxides.Use X-ray diffraction method (diffractometry) (XRD) to differentiate composite oxides.The data that obtain are listed in table 2.In table 2, LM is meant that sample is the diffracting spectrum that the complex Li-Mn-oxide of spinel structure does not have any impurity.
Table 2
Sample Li(Mn 2-xLi x)O 4In x Grain shape Average grain diameter (micron) Specific area (m 2/g) XRD analyzes
21 0 Hollow sphere 3.7 4.1 LM
22 0.002 Hollow sphere 3.7 4.0 LM
23 0.005 Hollow sphere 3.8 4.0 LM
24 0.010 Hollow sphere 3.7 4.1 LM
25 0.015 Hollow sphere 3.8 3.9 LM
26 0.018 Hollow sphere 3.8 4.0 LM
27 0.050 Hollow sphere 3.7 4.1 LM
28 0.100 Hollow sphere 3.7 4.0 LM
Then use the various composite oxides that make above to prepare storage battery as active material of cathode.
Exactly, the various composite oxides of 100 weight portions, 5 weight portion conductors (acetylene black) and 5 weight portion adhesives (polytetrafluoroethylene) are kneaded and be shaped in flakes.The pressurization of every kind of sheet is sticked on the SUS screen cloth dish of 17mm diameter and make negative electrode.
Then, use is same as the method for embodiment 1 but uses the negative electrode that makes above to prepare lithium storage battery.These storage batterys are carried out the discharge and recharge test identical with embodiment 1.Result of the test is listed in table 3.In table 3, the sample label of storage battery is same as the sample label as the composite oxides of active material of cathode.
Table 3
Sample Discharge capacity (mAh/g)
Initial value After 100 circulations After 200 circulations
21 134 116 109
22 134 119 112
23 133 118 114
24 132 121 115
25 131 120 116
26 130 120 116
27 121 111 107
28 102 99 97
By the data of table 2 and table 3 significantly as seen, with formula Li (Mn 2-xLi x) O 4Complex Li-Mn-oxide in lithium the replacement degree x of manganese is limited to greater than 0 (0＜x), can prevent the Jahn-Teller phase transformation, thereby prevent to contain after the charge and discharge cycles decline of the battery capacity of composite oxides, in addition, be limited to and be equal to or less than 0.10 when replacing degree x, preferably less than 0.02 o'clock, the storage battery that contains composite oxides can have higher initial capacity.Therefore, formula Li (Mn 2-xLi x) O 4In the x value should be preferably in the scope of 0＜x＜0.02 in 0≤x≤0.10.
In above-mentioned each embodiment, use the formula Li (Mn of spinel structure 2-xLi x) O 4Complex Li-Mn-oxide is as active material of cathode.But composite oxides are not limited in the present invention.Any passing through with the position of Cr, Ni, Fe, Co and/or Mg replacement part Mn derived from Li (Mn 2-xLi x) O 4The complex Li-Mn-oxide of other spinel structure also can be used among the present invention, and obtain identical result.
The atomizing pyrolysismethod that uses in the foregoing description prepares the active material of cathode (complex Li-Mn-oxide of spinel structure), also can use any other method to prepare composite oxide particle among the present invention.For example, the fine particle that is made by wet synthetic method can grow into the spherical secondary granule of hollow in atomizing dryer.
As described in detail above, lithium storage battery of the present invention contains the composite oxides of spinel structure as active material, the complex Li-Mn-oxide that it is characterized in that described spinel structure is hollow, the spherical secondary granule that is formed by the primary granule sintering, the average grain diameter of described secondary granule is the 1-5 micron, and specific area is 2-10m 2/ g.Therefore, lithium storage battery of the present invention has high capacity and good charge.
Be preferably, the composite oxides that are used as active material of cathode in storage battery of the present invention are by formula Li (Mn 2-xLi x) O 4Expression, 0≤x≤0.1 wherein, best 0＜x＜0.02.Use such composite oxides, can make lithium storage battery of the present invention have higher capacity and better charge.In addition, any passing through with the position of Cr, Ni, Fe, Co and/or Mg replacement part Mn derived from Li (Mn 2-xLi x) O 4The complex Li-Mn-oxide of other spinel structure also can be used among the present invention, and obtain identical result.

Claims (5)

1. lithium storage battery, comprise the complex Li-Mn-oxide that contains spinel structure negative electrode (3) as active material, the complex Li-Mn-oxide particle that it is characterized in that described spinel structure is hollow, spheric granules, it is the 1-5 micron that described particle surface has many dark hole and its average grain diameters of leading to its inside, and specific area is 2-10m 2/ g.
2. lithium storage battery as claimed in claim 1, the complex Li-Mn-oxide that it is characterized in that described spinel structure is by formula Li (Mn 2-xLi x) O 4Expression, wherein 0≤x≤0.1.
3. lithium storage battery as claimed in claim 1, the complex Li-Mn-oxide that it is characterized in that described spinel structure is by formula Li (Mn 2-xLi x) O 4Expression, wherein 0＜x＜0.02.
4. lithium storage battery as claimed in claim 1, the complex Li-Mn-oxide that it is characterized in that described spinel structure is by formula Li (Mn 2-xLi x) O 4Expression, wherein 0≤x≤0.1, and Mn is partly replaced by Cr, Ni, Fe, Co or Mg.
5. lithium storage battery as claimed in claim 1, the complex Li-Mn-oxide that it is characterized in that described spinel structure is by formula Li (Mn 2-xLi x) O 4Expression, wherein 0＜x＜0.02, and Mn is partly replaced by Cr, Ni, Fe, Co or Mg.
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